1. Field of the Invention
The invention is directed to the carbonylation of vinyl dihalides to produce novel amide compounds, olefinic esters, and the like.
2. Related Art
It is known to carbonylate halo-hydrocarbons such as benzyl chloride by reaction with carbon monoxmide and an alcohol at 100.degree. C. or below and at atmospheric pressure in the presence of an amine and a catalytic amount of a palladium catalyst to form esters.
An article entitled "Palladium-Catalyzed Carboalkoxylation of Aryle, Benzyl, and Vinylic Halides" by A. Schoenberg et al. appearing in The Journal of Organic Chemistry, Vol. 39, page 3318 (1974) discloses a process whereby aryl and vinylic bromides and iodides and benzyl chloride are each reacted with carbon monoxide and an alcohol at 100.degree. C. or below and at atmospheric pressures in the presence of a tertiary amine and a catalytic amount of a palladium-triphenylphosphine complex to form esters. The article does not disclose processes utilizing vinyl dihalides, nor the preparation of novel amines or esters of vinyl dihalide.
U.S. Pat. No. 3,116,306 discloses a process for preparing carboxylated organic compounds by reacting (1) an organic compound represented by the general formula R.sub.n Z in which R is an organic compound having at least one aliphatic radical or cycloaliphatic radical, Z is SO.sub.4, X, X.sub.2 or R'SO.sub.3, X being a halogen and R' is alkyl, alkenyl, cycloalkyl, aryl or aralkyl, where n is 1, Z is X, X.sub.2 or R'SO.sub.3, and when n is 2, Z is SO.sub.4, the Z substituent being attached to an aliphatic or cycloaliphatic primary or secondary carbon atom; (2) carbon monoxide; (3) a salt of a metal hydrocarbonyl of the group consisting of cobalt hydrotetracarbonyl and iron dihydrotetracarbonyl and (4) a material of the group consisting of water, alcohols, phenols, mercaptans, ammonia, hydrazine, primary organo-nitrogen bases and secondary organo-nitrogen bases. This patent discloses that tertiary amines such as dicyclohexylethylamine have been found to be of general use in the process of the invention.
U.S. Pat. No. 4,480,121 describes the reaction of a hydrocarbon stream with a hydrogen halide to produce 2halo-1-alkenes. The invention further comprised preparing acrylate esters by contacting the 2-halo-1-alkene with carbon monoxide and an esterifying agent.
In a paper entitled "Carboxymethylation of Organic Halides by Palladium Complexes under Mild Conditions" by Masanobu Hidai et al. appearing in the Bulletin of the Chemical Society of Japan, Vol. 48 (7), pages 2075-2077 (1975) there is disclosed the attempted carboxymethylation of various organic dihalides to their corresponding esters under what are described as very mild conditions. The article discloses that the carbonylation of organic dihalides was unsuccessful since they did not afford corresponding esters. The amine used in the process and those disclosed were secondary amines.
In none of the above references is there taught, suggested or shown the carbonylation of organic dihalides to produce corresponding amides or esters using secondary or tertiary amines.
U.S. Pat. No. 4,128,554 discloses the preparation of carboxylic acid amides from organic halides. The process disclosed is the reaction of an aryl, heterocyclic, or vinylic halide and substituted derivates thereof with a primary or secondary amine and carbon monoxide in the presence of a palladium catalyst and, if necessary, a tertiary amine at temperatures of about 20.degree.-150.degree. C. and at least a half atmosphere of pressure. There is no disclosure relevant to using vinyl dihalides in the process disclosed.
A paper entitled, "Synthesis of Diynes, Alpha, BetaUnsaturated Monoacids, and Diacids by the Selective Palladium (O)-Catalyzed and Phase Transfer Catalyzed Reactions of Vinylic Dibromids" by Galamb et al. appearing in Organometallics, 1983, pp. 801-805, teaches the alpha and beta-unsaturated monoacids and diacids were the products formed by reacting vinylic dibromides with carbon monoxide using a zero valent palladium catalyst.